Compounds having a trichloromethylic end group having a juvenile hormone action on insects and acaricide activity

ABSTRACT

New compounds are disclosed which have a juvenile hormone action on insects and also exhibit acaricide action. More particularly, said new compounds are unsaturated aliphatic compounds having a trichloromethyl end group and the other end group of which is a phenol group which may be substituted and/or condensed, and which are capable of hindering the growth of insects from the larval to the adult stage and also exhibit an acaricide action on both adult acari and their eggs. 
     Processes for the production of the new compounds of the invention are also disclosed.

THE PRIOR ART

Application Ser. No. 540,167 filed Jan. 10, 1975, now U.S. Pat. No.4,000,312, (corresponding to Italian applications Nos. 19,332 A/74 and28,583 A/74) discloses unsaturated aliphatic compounds having a vinyldichloro- or trichloro-substituted end group of the general formula##STR1## wherein: X is H or Cl;

M, n, p, q, r, s, is 0; 1; or 2;

R which may be the same or different represent H, lower alkyls possiblybranched and/or substituted; p1 A, B is H or A+B represents a furtherbond; ##STR2## wherein: R¹ is alkyl or lower alkenyl possibly branchedand/or substituted, or --C₆ H₄ Wμ wherein μ is 1; 2; or 3 and W=H,halogen, lower alkyl like R¹, alkoxyl, thioalkyl, carbalkyl,carboxyalkyl, --NO₂, phenyl, a heterocyclic nucleus possibly condensedat the benzenic ring in 3, 4; or an aminic group possibly substitutedwith substituents forming open or closed chains in cycle with nitrogen;

R², r³, the same or different represent H, possibly substituted loweralkyls, or

R² +r³ forms with N and/or additional heteroatoms, a cycle of 5, 6, or 7atoms; and

Y is H, lower alkyl, lower alkoxyl, --OH, --O-metal, cycloalkyl or aryl.

Said compounds display a good juvenile hormone activity (such, that is,to inhibit the growth of the insects from the larval to adult stage).However, because the dichloroor trichloro-vinyl end group, often nearother unsaturated groups, tends to be unstable, those comounds may bedifficult to use under particular conditions.

THE PRESENT INVENTION

We have now found, and this is one object of the present invention, thatcompounds having a trichloromethyl end group and of the general formula:##STR3## wherein: R is H or CH_(3;)

R¹ is CH₃ or C₂ H₅ ;

p is 0 or 1;

q is 1 or 2 (when p=1, q must be 1);

X is O or S;

n is 1, 2 or 3;

Z is H, halogen, alkyl with from 1 to 5 carbon atoms; alkoxy with C₁ -C₅; thioalkyl with C₁ -C₅ ; carboalkyl with C₁ -C₅ ; carboxyalkyl with C₁-C₅ ; NO₂ ; phenyl; a condensed heterocyclic nucleus with a benzoicring; ##STR4## wherein R² and R³, the same or different, are H or analkyl with C₁ to C₅ ; CN; are possessed of both good juvenile hormoneactivity and acaricide effectiveness.

The method of preparing the present compounds, which is also a featureof this invention, involves reactions which are partly known and whichstart from materials of petrochemical origin that are widely available.

The first series of rections has the object of preparing ketones of thegeneral formula: ##STR5## (wherein R, R¹, p and q have the same valuesas in formula I). The schemes are the following: ##STR6##

According to the 1st scheme, the condensation reaction is carried outbetween carbon tetrachloride and an alkyl-vinylketone according to aRedox-reaction of the type described by Vofsi & Ascher in the JournalChemical Society 1963, 3921. Thereby aduct (3) is obtained which may behydrogenated to the saturated ketone (4), or dehydrohalogenated to theunsaturated α-βketone (5), in its turn hydrogenatable to (4).

According to the 2nd scheme, the carbon tetrachloride is added to a1,3-diene (6) in order to obtain the aduct (7); this latter, condensedwith the β-ketoester (8), gives the intermediate (9) which, by asuccessive hydrolytic decarboxylation, supplies the γ,δ -unsaturatedketone (10).

According to the 3rd scheme, the carbon tetrachloride is condensed withvinyl acetate to obtain the intermediate (11), which latter, by alkalinehydrolysis, is converted to aldehyde (12). The crotonic typecondensation of the aldehyde with acetone yields the α,β -unsaturatedketone (13) which, by hydrogenation, may be converted to the saturatedketone (14).

The compounds of formula (I) are obtained from the ##STR7## (2) Theunsaturated alcohol 15 may also be obtained by reacting the startingketone with alkaline acetylide: ##STR8##

The products (16) and (17) are then obtained as shown above.

Among others, there have been prepared the following compounds of theformulae given, and which are further identified by our referencenumber, the NMR spectrum and, in some instances, other characteristics:

(1) 4-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-tert.butylbenzene(our reference M 5915). ##STR9##

NMR δ = 1.25 3--CH₃ ; 1.78 --CH₃ ; 2.24 --CH₂ --CH₂ 3.25 CCl₃ --CH₂ ;4.60 --CH₂ --0; 5.55, 3 vinylic H; 6.7-7.3, 4 aromatic H in p.p.m.

(2) 4-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)acetophenone (ourref. M 5916). ##STR10##

NMR δ = aliphatic portion analogous to that of compound (1) ##STR11##(3) 1-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-2,3-dimethylbenzene(our ref. M 5917). ##STR12##

NMR δ = aliphatic portion analogous to that of compound (1)

(4) 4-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-ethyl benzoate (ourref. M 5918). ##STR13## NMR δ = aliphatic part analogous to that ofcompound (1); 1.45 --CH₂ --CH₃ ; 4.49--O--CH₂ ; 7.0-8.05, 4 aromatic H.

(5) 1-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-3,5-dimethylbenzene(our ref. M 5919). ##STR14##

NMR δ = aliphatic portion analogous to that of compound (1); 2.18, 2CH₃,6.35-6.45, 3 aromatic H.

(6) 1-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-3,4-dimethylbenzene(our ref. 5920). ##STR15##

NMR δ = aliphatic portion analogous to that of compound (1);

(7) 4-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-methylbenzoate (ourref. M 5921). ##STR16##

NMR δ = aliphatic portion analogous to that of compound (1); 4.05--OCH₃; 7.0-8.05, 4 aromatic H.

(8) 3-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-methylbenzene (ourref. M 5923). ##STR17##

NMR δ = aliphatic portion analogous to that of compound (1); 2.25 CH₃ ;6.60-7, 4 aromatic H.

(9) 3-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-methoxybenzene (ourref. M 5924). ##STR18##

NMR δ = aliphatic portion analogous to that of compound (1); 3.75 OCH₃,6.5-7.30, 4 aromatic H.

(10) 3-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-nitrobenzene (ourref. M 5925). ##STR19##

NMR δ = aliphatic portion analogous to that of compound (1); 7.20-7.60,4 aromatic H.

(11) 4-(9,9,9-trichloro-3-methyl-nona-2,6-dienyloxy)-methylthiobenzene(our ref. M 5926). ##STR20##

NMR δ = aliphatic portion analogous to that of compound (1); 2.42,S--CH₃ ; 6.75-7.22, 4 aromatic H.

(12)1-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-3,4-methylendioxybenzene(our ref. M 6239). ##STR21##

NMR δ 1.75, --CH₃ ; 1.88, --CH₃ ; 2.23, --CH₂ --; 3.35CCl₃ --CH₅ ; 4.60,CH₂ --O--; 5.5, 2H; 5.80, --O--CH₂ --O; 6.15-6,7,3 aromatic H.

(13) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)ethylbenzene(our ref. M 6241). ##STR22##

NMR δ = aliphatic portion analogous to that of compound (12); 1.19,CH₂--CH₃ ; 2.58, --CH₂ --CH₃ ; 6.75 - 7.05, 4 aromatic H.

(14) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)acetophenone(our ref. M 6242). ##STR23##

NMR δ = aliphatic portion analogous to that of compound (12); 2.50,O--CH₃ ; 6.80-7.80, 4 aromatic H.

(15) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)isopropylbenzene(our ref. M 6243). ##STR24##

NMR δ = aliphatic portion analogous to that of compound (12); 1.20, 2CH₃ ; 2.8, --CH(CH₃)₂ ; 6.80-7.05, 4 aromatic H.

(16) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)n.propylbenzene(our ref. M 6244). ##STR25##

NMR δ = aliphatic portion analogous to that of compound (12); 0.70, CH₃; 1.55, CH₂ --CH₃ ; 2.45, --CH₂ --CH₂ --CH₃ ; 6.7-6.9, 4 aromatic H.

(17) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)methylbenzene(our ref. M 6245). ##STR26##

NMR δ = aliphatic portion analogous to that of compound (12): 2.30,--CH₃ ; 6.75-7.1, 4 aromatic H.

(18) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-methoxybenzene(our ref. M 6246). ##STR27##

NMR δ0 = aliphatic portion analogous to that of compound (12);3.65,--O--CH₃ ; 6.60, 4 aromatic H.

(19)4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)thiomethylbenzene(our ref. M 6248). ##STR28##

NMR δ = aliphatic portion analogous to that of compound (12);2.40,--S--CH₃ ; 6.75-7.20, 4 aromatic H.

(20) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)nitrobenzene(our ref. M 6249). ##STR29##

NMR δ = aliphatic portion analogous to that of compound (12).

(21) 3-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)anisole (ourref. JH 22). ##STR30##

NMR δ = aliphatic portion analogous to that of compound (12);3.75,--O--CH₃ ; 6.50-7.30, 4 aromatic H.

(22 ) 2-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-5-tert.-butyl-chlorobenzene (our ref. JH 12) ##STR31##

NMR δ0 = aliphatic portion analogous to that of compound (12) 1.313--CH₃ ; 6.70-7.40, 3 aromatic H. Elementary analysis: C=57.2(57.5);H=6.5(6.38); Cl = 31.5 (32.4)%.

(23) 3-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)benzonitrile(our ref. JH 8). ##STR32##

NMR δ = aliphatic portion analogous to that of compound (12); 7.30,aromatic 4H. Elementary analysis: C=57.7(58.04); H=5.35(5.38); Cl = 27(28.6)%.

(24) 3-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-acetophenone(our ref. JH 4). ##STR33##

NMR δ = aliphatic portion analogous to that of compound (12);2.54--CO--CH₃ ; 7.0-7.5, 4 aromatic H. Elementary analysis:C=59.0(58.54); H=5.9(5.90); Cl = 26.5 (27.34)%.

(25) 3-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxyethylbenzene (ourref. JH 7) ##STR34##

NMR δ = aliphatic portion analogous to that of compound (12); 1:24,--CH₂--CH₃ ; 2.65,--HC₂ CH₃ ; 6.75-7.38, 4 aromatic H. Elementary analysis:C=61.0(60.72); H=6.8(6.66); Cl = 26.7 (28.36).

(26) 4-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-ethyl benzoate(our ref. JH 5): ##STR35##

NMR δ = aliphatic portion analogous to that of compound (12); 1.38--OCH₂ --CH₃ ; 4.50--OCH₂ --CH₃ ; 6.95 - 8.07, 4 aromatic H.

(27) 4(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-benzonitrile##STR36##

NMR δ = aliphatic portion analogous to that of compound (12); 7.01 -7.61, 4 aromatic H. Elementary analysis: C=57.5 (57.98), H=5.4 (5.37),N=3.7 (3.76), Cl=27.7 (28.6).

The activity of compounds (1) to (27) varies according to the compoundand to the species on which they have been tested, as do others of thesame series and comprised within this invention. Thus, for instance, thecompound identified by us as JH 8 has a good juvenile hormone activityat 200 γ/insect on Spodoptera littoralis, while its activity is null atthe same concentrations on Tenebrio molitor.

On the contrary, compound M 6249 is highly active at concentrations of20 γ/insect on Tenebrio molitor, while it is inactive at 200 γ/insect onSpodoptera littoralis.

Also the acaricide activity varies from compound to compound and,depending on whether tested on adult insects or on the eggs.

Compound M 5918, for instance, shows a certain acaricide activity at aconcentration of 0.1% on the eggs of Tetranichus urticae, while it isinactive at the same concentrations on the adult insect. On thecontrary, compound M 5926 is more active on the adult insect than on theeggs at the same concentrations.

The hormone juvenile activity has been tested, under the conditionsdescribed in Example 13, on the following species: Tenebrio molitor,Pieris brassicae, Spodoptera littoralis, for topical treatment on pupaeand larvae; Anagasta kueniella, Tribolium confusum, Aedes aegypti forthe treatment of the habitat or of the substrate on which the larvaewere growing. For Musca domestica, the active principle was applied onthe adults and there were then ascertained, after given periods of time,the effects on the undisclosed eggs, the larvae that had become pupae,and then the born adults.

The acaricide activity was tested on Tetranychus urticae, both on theadult insect as well as on the eggs, as described in Example 14.

The following examples are given to better illustrate this invention,and are not intended as limiting.

EXAMPLE 1 Preparation of mixture (E)-1,5,5,5-tetrachloro-2-methyl-pent-2-ene, and (E)-1,5,5,5-tetrachloro-3-methyl-pent-2-ene.

Reaction: ##STR37##

Into a stainless steel 500 ml autoclave was loaded a mixture of CCl₄(153 g, 1 mol), isoprene (34.1 g - 0.5 mol), CH₃ --CN (39 g - 0.94 mol),CuCl₂ ·2H₂ O (0.85 g) and n-butylamine (0.875 g).

After 6 hours at 130° C., the autoclave was cooled down and the contentwas recovered. From two identical tests there were obtained 433 g of adark oil which, after concentration at reduced pressure, washing withwater and drying, yielded 213 g of a mixture containing 17% by weight of(E) -1,5,5,5-tetrachloro-2-methyl-pent-2-ene and 66% b.w. of (E)-1,5,5,5-tetrachloro-3-methyl-pent-2-ene, this mixture having a boilingpoint of 116°-118° C. at 20 mm Hg.

The separation of the two isomers was carried out by gas chromatographyand the identification was established through the NMR spectrum (NuclearMagnetic Refraction).

EXAMPLE 2 Preparation of (E)-2-acetyl-7,7,7-trichloro-5-methyl-hept-4-ethyl enoate (Scheme A).

Reaction: ##STR38##

Into a 1 lt flask were loaded 250 ml of anhydrous tetrahydrofurane, 9.8g (0.224 mol) of NaH in a 55% b.w. mixture in mineral oil.

Under gentle stirring and being careful not to exceed 33° C., there wereintroduced into the autoclave 292 g (0.224 mol) of ethyl acetoacetate,and then 55 g of the mixture of isomers of Example 1 (respectively0.0867 mol and 0.161 mol). The resulting mass was refluxed for 8 hoursand was then left to rest at room temperature for 12 hours.

The tetrahydrofurane was then evaporated at reduced pressure and theresidue was poured into water. An organic phase separated and wascombined with the extracts from the water with CH₂ Cl₂. After drying theextracts in organic solvent on NaSO₄ and after evaporation under vacuum,there was obtained, by distillation under vacuum of the residue, an oil(42 g, 0.133 mol) consisting of(E)-2-acetyl-7,7,7-trichloro-5-methyl-hept-4-ethyl eonate having a b.p.of 108°-110° C. at 0.001 mm Hg.

The product, purified by gas chromatography, was identified on the basisof the NMR spectrum.

EXAMPLE 3 Preparation of (E)-8,8,8-trichloro-6-methyl-oct-5-en-2-one.##STR39##

37.5 g (0.119 mol) of 2-acetyl-7,7,7-trichloro-5-methyl-hept-4-ethylenoate were added dropwise into a solution of 7.8 g of 85% KOH in 100 mlof H₂ O. This mixture was then subjected to stirring at room temperatureunti dissolution of the ester (about 4 hours), and then extracted withethyl ether to remove the unreacted ester.

The aqueous phase was then acidified with 30 g of H₂ SO₄ at 50%concentration, refluxed for 1 hour and, after cooling down, extractedwith ether.

The ether extracts, after washing with water and drying on anhydrous Na₂SO₄, were evaporated under vacuum. The residue, distilled under vacuum,gave an oil (11.6 g, 0.0475 mol) with a b.p. of 70°-72° C. at 0.1 mm Hg,besides 22.6 g of unreacted ketoester. The oil, after purification bygas chromatography, was identified as(E)-8,8,8-trichloro-6-methyl-octo-5-en-2-one on the basis of the NMRspectrum.

EXAMPLE 4 Preparation of9,9,9-trichloro-3,7-dimethyl-nona-1,6-diene-3-ole. ##STR40##

Into a 2,000 ml flask were introduced 33 g of magnesium shavings whichwere covered with 360 ml of anhydrous tetrahydrofurane. Under stirringand in a nitrogen atmosphere, there were added dropwise 127 g of vinylbromide in 320 ml of anhydrous tetrahydrofurane, so that the temperaturedid not exceed 40°-50° C.

Once the addition had been completed, the mass was reflux-heated for 30minutes; thereupon the temperature was brought down to room temperatureand into it was introduced dropwise a solution of 286 g of(E)-8,8,8-trichloro-6-methyl-oct-5-en-2-one in 220 ml of anhydroustetrahydrofurane, taking care not to exceed 30° C. After the operationhad been accomplished, the reaction mixture was left to rest at roomtemperature for 24 hours. After this the reaction mixture was hydrolizedwith ice and ammonium chloride. Then it was decanted, extracted withethyl ether, and the extract was washed with water and dried onanhydrous Na₂ SO₄.

After evaporation of the solvent and distillation, there were obtained173 g of a product boiling at 90°-95° C. at 0.001 mm Hg, and which wasidentified as 9,9,9-trichloro-3,7-dimethyl-nona-1,6-dien-3-ole by meansof the NMR.

EXAMPLE 5 Preparation of1-bromo-9,9,9-trichloro-3,7-dimethyl-nona-2,6-diene.

Reaction: ##STR41##

To 194-5 g of a 48% solution of HBr in water there were added 105.2 g ofthe alcohol of the preceding example at 0-5° C.

After stirring for 1 hour at 0° C., the reaction mixture was poured intowater and ice and the organic layer was separated and added to the etherextract of the aqueous phase.

The mixture was then washed with a 10% b.w. aqueous solution of Na₂ CO₃and, then, with water, until reaching neutrality. Thereupon, it wasdried on Na₂ SO₄, the ether was evaporated under reduced pressure, anddistillation was carried out under vacuum. Thereby were obtained 110 gof oil having a b.p. of 100°-105° C. at 0.05 mm Hg.

On NMR spectography examination, said oil was found to consist of 70%b.w. of isomer 1-bromo-9,9,9-trichloro-3,7-dimethyl-nona-(E)-6-diene andof 30% b.w. of isomer1-bromo-9,9,9-trichloro-3,7-dimethyl-nona-(Z)-2-(E)-6-diene.

EXAMPLE 6 Preparation of1-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-3,4-methylendioxybenzene(our ref. 6239).

Reaction: ##STR42##

Under stirring and in an inert atmosphere, 20.6 g of3,4-methylene-dioxy-phenol were mixed with a suspension of K₂ CO₃ (20.6g) in methylethylketone (200 cc). The mixture was cooled down to 0° C.and additioned with 50 g of the bromide of the preceding Example. Themass was then stirred for 48 hours at 0° C. after which the reactionmixture was poured over ice.

The organic residue that separated and the ether extracts of the aqueousphase, combined, were decolored with active coal, and concentrated atreduced pressure.

Thereby were obtained 60 g of1-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyloxy)-3,4-methylendioxybenzene.The NMR spectrum, compatible with the structure given, was obtained on aproduct purified by a preparatory thin-layer chromatography (carrier:Merck silica gel; solvents: n-hexane-ethyl ether 90:10).

EXAMPLE 7 Preparation of 4,5,5,5-tetrachloro-pentan-2-one.

Into a Pfaudler 1/2 gallon autoclave was loaded a mixture ofmethylvinylketone (213 g), CH₃ CN (195 g), CCl₄ (925 g), CuCl₂ ·2H₂ O(5.1 g) and n-butylamine (5.25 g). This reaction mixture was heated for5 hours at 120° C. under constant stirring. During this period theinternal pressure of the autoclave changed from 3.5 kg/sq.cm to 3.1kg/sq.cm. After removal, at reduced pressure, of the greatest part ofthe volatile substances, the residue was washed with water, reunitedwith the ether extracts of the aqueous phase, dried (on Na₂ SO₄) anddistilled to yield 290 g of 4,5,5,5-tetrachloro-pentan-2-one (boilingpoint 108°-110° C. at 18 mm Hg).

EXAMPLE 8 Preparation of 5,5,5-trichloro-pentan-2-one.

A solution of 25 g of ketone (prepared as above) in 25 ml of glacialacetic acid was added to a suspension of 12.5 g of Zn powder in 50 ml oftetrahydrofurane (THF).

The addition was carried out taking care not to exceed 30° C. After 1hour of stirring at the reflux temperature of the THF, the reactionmixture was hydrolyzed with water. After distillation the organicresidue yielded 13 g of 5,5,5-trichloropentan-2-one (b.p. 83°-85° C. at16 mm Hg).

The NMR spectrum in CCl₄ was 67 = 2.185 (3H, s, CH₃), 2.932 (4H, t J ≃2.7 Hz, --CH₂ --CH₂ --).

EXAMPLE 9 Preparation of 6,6,6-trichloro-3-methyl-hex-1-en-3-ole.

Using the procedure described in Example 4 there were obtained, from 7 gof 5,5,5-trichloropentan-2-one, 0.9 g of Mg, 4.35 g of vinyl bromide and75 ml of THF, 5.7 g of 6,6,6-trichloro-3-methyl-hex-1-en-3-ole (b.p.105-107° C. at 18 mm Hg).

EXAMPLE 10 Preparation of 1-bromo-6,6,6-trichloro-3-methyl-hex-2-ene.

Using the procedures of Example 5 there were obtained, from 5.7 g of6,6,6-trichloro-3-methyl-hex-1-en-3-ole, 6 g of1-bromo-6,6,6-trichloro-3-methyl-hex-2-ene.

By elementary analysis and examination of the NMR spectrum (CCl₄) theproduct was identified by the following data: δ = 1.7 (s, CH₃ of thetrans-isomer), 1.76 (s, CH₃ of the cis-isomer), 2.4-2.9 (4H, m, CH₂CH₂), 3.9 (2H, d J ≃ 8 Hz, --CH₂ Br), 5.5 (1H, t J ≃ 8 Hz,═CH--).

EXAMPLE 11 Preparation of1-(6,6,6-trichloro-3-methyl-hex-2-enyloxy)-3,4methylen-dioxybenzene.

Example 6 was repeated but using 5 g of1-bromo-6,6,6-trichloro-3-methyl-hex-2-ene. There were obtained, afterseparation in a column chromatography, 3 g of1-(6,6,6-trichloro-3-methyl-hex-2-enyloxy)-3,4-methylendioxy-benzenewhich by elementary analysis and examination of the NMR spectrum, wasidentified as follows: [CCl₄, δ = 1.8 (3H, s, Me), 2.4-2.9 4H, CH, CH₂CH₂), 4.35 (2H, s, OCH₂ O), 6.15 (1H, dd J ≃ 7.5 and J ≃ 2 Hz, aromaticH (6)), 6.35 (1H, d J ≃ 2 Hz, aromatic H (2)), 6.56 (1H, d J ≃ 7.5 Hz,aromatic H (5)) ].

EXAMPLE 12 Preparation of1-bromo-9,9,9-trichloro-3-methyl-nona-2,6-diene.

From 65 g of (E)-1,1,1-trichloro-oct-3-en-7-one, prepared as indicatedby W. J. Pyne in Journal of Organic Chemistry 27, p. 3483, 1962, andoperating as in Example 4, there were obtained 30 g of9,9,9-trichloro-3-methyl-nona-1, 6-dien-3-ole, which when treated withan excess of 40% HBr as in Example 5, resulted in 35 g of an oil havinga boiling point of 100°-102° C. at 0.05 mm Hg.

Examination of the NMR spectrum showed that said oil consisted of amixture, in a ratio 70:30, of forms E and Z of the1-bromo-9,9,9-trichloro-3-methyl-nona-2,6-diene.

EXAMPLE 13 Preparation of1-(9,9,9-trichloro-3-nona-2,6-dienyloxy)-3,4-methylendioxybenzene.

From 4 g of allyl bromide, prepared as described in the precedingexample and operating with the same stoichiometric ratios and inaccordance with Example 6, there were obtained 3 g of the juvenoid ofthe title of this example (b.p.: 138°-145° C. at 0.001 mm Hg).

EXAMPLE 14

The juvenile hormone activity of the products were tested in Tenebriomolitor, Tribolium confusum, Pieris bassicae, Spodoptera littoralis,Aedes Aegypti, Musca domestica.

The conditions under which the tests were conducted are reported below,species by species:

(1) Tenebrio m.

0-24 hour aged pupae were treated by topical application on theatenpenultimate urosternite with an acetone solution of the product (2cu. mm). The results were surveyed after about 9 days, when the insectsof the witness group had completed their emergence from the cocoons.

(2) Pieris b.

Larvae of the last age were treated by topical application on the firsturosternites with an acetone solution of the product (2 cu. mm).

Survey of the results was made about every 5 days up to the completeemergence from the cocoons of the adults in the witness group.

(3) Spodoptera l.

Larvae of the last age were treated by topical application on the firsturosternites with an acetone solution of the product (2 cu. mm).

Survey of the results was made about every 5 days up to the completeemergence from the cocoons of the adult insects in the witness group.

(4) Anagasta k.

5 g of maize meal were uniformly treated with an acetone solution of theproduct. 24 hours after the treatment, the meal (or flour) was infestedwith 21 days old larvae.

The survey of the results was made every 3-4 days starting from thefirst appearance of the adult insects until the end of the emergencefrom the cocoons in the witness group.

(5) Tribolium c.

5 g of wheat meal were uniformly treated with an acetone solution of theproduct. 24 hours after the treatment the flour was infested with 22days old larvae.

Evaluation of the results was made about 45 days later, when the insectsof the witness group had completed emergence from the cocoons.

(6) Musca d.

5 g of sugar and 5 g of a mixture consisting of sugar, milk and egg yolkpowder were treated separately with an acetone solution of the product.

After evaporation of the solvent, the sugar and the mixture wereintroduced separately into two beakers together with 50 adult flies, 25males and 25 females.

Successively, to the flies fed with the treated sugar was given theabove said egg-based mixture that had not been treated, however, withthe compounds of this invention. After the first egg laying, 100 eggswere transferred to the nutritive substratum (pabulum). After 2 daysthere was determined the percentage of disclosed eggs; after a further 5days and pupae were gathered together and counted and 4 days later thepercentage of adults which emerged from the cocoons was established.

(7) Aedes aegypti.

3 cc of an acetone solution of the product were added to 297 cc of tapwater into which were successively transferred 25 larvae, four days old,and which were supplied with suitable food. The results were surveyedevery 2-3 days until the end of the emergence from the cocoons of thewitness group. Evaluation criteria of the activity for the insects oftests 1-4, 5 and 7.

As activity index there was adopted the percent ratio of deadindividuals, misshapen and abnormal individuals with respect to thenumber of treated individuals, according to the following formula:##EQU1## Evaluation criteria on the results of the test on Muscadomestica (6).

As activity index was adopted the percent ratio of the undisclosed eggswith respect to the total of eggs laid by the insects treated, using thefollowing formula: ##EQU2##

The results of the test referred to herein are reported in Table I.

                                      TABLE I                                     __________________________________________________________________________    JUVENILE HORMONE ACTIVITY OF THE COMPOUNDS OF THIS INVENTION                                  Tribolium conf.                                                                       Pieris                                                                             Spodoptera                                                                          Anagasta                                                                            Aedes                                                                             Musca                                   Tenebrio molitor                                                                       p.p.m.  brassicae                                                                          littoralis                                                                          kuehniella                                                                          aegypti                                                                           domestica                               γ/ins.                                                                           %       γ/ins.                                                                       γ/ins.                                                                        p.p.m.                                                                              p.p.m.                                                                            adults %                         PRODUCT                                                                              200  20  2000    200  200   2000  20  1                                __________________________________________________________________________    M 6239 100  100 98      100  100   100   100 100                              M 6241 100  100 100     --   100   76    49  1                                M 6242 100  100 100     100  34    70    35  36                               M 6249 100  55  100     --   0     52    38  2                                M 5926 71   --  48      --   0     94    31  40                               M 5921 0        18      --   33    83    30  80                               JH 3   0        11      0    0      5    57  57                               __________________________________________________________________________

EXAMPLE 15 Acaricide activity on Tetranychus articae adults and eggs.

The conditions under which the tests were conducted are as follows:

Eggs: Small discs of bean leaves were infested with acari eggs and thentreated by sprinkling with an aqueous suspension of a 0.1% concentrationof the product under examination. the mortality rate (untreated smallleaves discs = 0) is recorded in Table II.

Adults: Small discs of beam leaves were infested with acari adults andthen treated with an aqueous dispersion of a 0.1% concentration of theproduct under examination.

The death rate (untreated small discs = 0) was recorded in Table II.

TABLE II Acaricide activity on Tetranychus urticae adults and eggs byproducts of the invention at 0.1% concentration

    ______________________________________                                                    Tetranychus urticae                                               PRODUCT      Adults         Eggs                                              ______________________________________                                        M 6239       18             15                                                M 6242       24              8                                                M 6244       27             80                                                M 5925       38             49                                                M 5926       79             64                                                M 5915       48             11                                                M 5917       87             83                                                M 5920       66             83                                                ______________________________________                                    

We claim:
 1. Compounds of the general formula: ##STR43## in which R is Hor CH_(3;) R' is CH₃ or C₂ H₅ ; p is 0 or 1; q is 1 or 2 (when p is one,q must be 1); n is 1, 2 or 3; and
 2. The compound having the formula##STR44## i.e.:1-(9,9,9-trichloro-3,7-dimethyl-nona-2,6-dienyl-oxy)-3,4-methylendioxybenzene.3. The compound1-(6,6,6-trichloro-3-methyl-hex-2-enyloxy)-3,4-methylendioxybenzene. 4.The compound1-(9,9,9-trichloro-3-nona-2,6-dienyloxy)-3,4-methylendioxybenzene.
 5. Aninsecticide composition containing at least one compound of the formulaof claim 1, and which has both an effective amount of juvenile hormoneactivity and an effective amount of anti-acari activity.
 6. The methodof combatting noxious insects, which comprises spreading a compositionthe essential constituent of which is at least one compound of theformula of claim 1, in an amount of at least 0.01 p.p.m. , or in anamount of at least 0.002 γ/insect, on the insects, the habitat thereof,the food thereof, the eggs thereof, the pupae or larvae, or the food ofthe pupae or larvae.